Azo compounds and material colored therewith



Patented Dec. 24, 1940 UNITED STATES AZO COMPOUNDS AND MATERIAL COLORED THEREWITH Joseph B. Dickey, Rochester, N. =-Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application February23, 1939,

' Serial No. 258,021

15 Claims.

This invention relates to the art ofdyeing or coloring. More particularly, it relates to new azo dye compounds and the application of the nuclear non-sulfonated dye compounds for the coloration of organic derivatives of cellulose, particular- 1 1y textile materials made of or containingan or-,

ganic derivative of cellulose, by dyeing, printing, stenciling, or like methods.

Organic derivatives of cellulose are characterized by an ,indifierent aflinity for the usual cotton and wool dyes especially the ordinary water soluble dyes. Because of this, it has been necessary to develop new dye compounds suitable for the dyeing or coloration of material-s, such as textile materials, made of or containing an organic derivative of cellulose. It is, accordingly, an object of my invention to provide a new class of azo dyes suitable for therdyeing or coloration of organic derivatives of cellulose. Another object is to provide a process for the coloration of organic derivatives of cellulose in which the dye or dyes are applied directly from an aqueous suspension to the material undergoing coloration. A further object is to produce dyeings on organic derivatives of cellulose which are of good fastness to light and washing. Other objects will hereinafter appear. 1

Typical organic derivatives of cellulose include the hydrolyzed as well as the unhydrolyzed celderivatives of cellulose such as those justrmentioned.

The azo dye compounds of the general formula:

v R N=N--R1 wherein R. represents the residue of an-aryl nucleus of the benzene series containing two groups, wherein R2 represents an alkyl group, an allyl group, or a cycloalkyl group, one in ortho and one in para position to the azo bond and R my invention have lulose organic acid esters such as cellulose acetate,

represents the residue of an aromatic, a hydroaromatic, or a heterocyclic coupling component.

.While my invention relates broadly to azo- ,dye compounds having the above general formula, it relatesmore particularly to theuazocompounds having the general formulae:

and

wherein R2 and R3 I each represents an alkyl group, an allyl group, or a cycloalkyl group, R1 represents an aromatic nucleus, a hydroaromatic nucleus,.or.a heterocyclic nucleus and X represents a monovalent substituent such as, for example, a nitro group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a $111. fonamide group, a carboxamide group, or an alkyl sulfone group. Advantageously R2 and R3 are alkyl. Similarly, R1 is advantageously the residue of an aryl coupling component of the benzene series and more particularly the residue of a'hydroxyalkylamine of the benzene. series.-

The azo dye compounds of my invention can be prepared by diazotizing a primary aromatic amine having the general formula RNH2 wherein R represents the residue of an aryl nucleus of the benzene series containing two groups, wherein R2 represents an alkylgroup, an allyl group, or a cycloalkyl group, one in ortho and one in para positionto the amino group and coupling the-diazonium compound obtainedwith an aromatic, a hydroaromatic or a teterocyclic coupling. compound.

'As previously indicated the nuclear non-sulfonated dye compounds of my invention consti-i tute valuable dyes for the coloration of organic derivatives of cellulose such as those hereinbefore mentioned yielding various shades .thereon of good fastness to light and washing. These nuclear non-sulfonated dye compounds likewise possess application for the dyeing of wool and silk and yield generally similar shades on these materials tion of the azo dye compounds of my invention? Ercample 1 17.7 grams of 1-amino-2,4-phenyldimethylketone are added to 200 cc. of water to which has been added 30 cc. of 36% hydrochloric acid. The resulting solution is cooled by the addition of ice, for example, to about 0-50 C. and the amine is diazotized by the addition, with stirring, of 6.9

recovered by filtration, washed with water and dried. The dye compound obtained colors cellulose acetate silk a greenish-yellow shade.

Example 2 14.2 grams of l-methyl barbituric acid,

O=CNCH:

H2O C=O O=ONH2 are dissolved in 200 cc. of water containing 30 grams of sodium carbonate. The resulting solution is cooled to a temperature approximating 0-10 C. and the diazonium solution prepared as described in Example 1 is addedwith stirring. Upon'completion of the-coupling reactionwhich takes place, the mixture is made acid to litmus by the'addition of hydrochloric acid and the dye compound formed is recovered by filtration, washed with water and dried. The-dye compound obtained colors cellulose acetate silk a greenish-yellow shade. I

Example 3 19.1 grams of 1-amino-2-methyl-4-ethylphenyl diketone CZHE EQNHZ are diazotized as described in Example 1.

. 13.7 grams of cresidine 'are dissolved in a cold dilute hydrochloric acid solution and the resulting solution is cooled, if necessary, to a temperature of 010 C. The diazonium solution prepared as described above is added, with stirring, to this cooled solution and after its addition the mixture is permitted to stand a short time following which it is slowly made neutral to Congo red paper by the addition of sodium acetate. Upon completion of the coupling reaction, the dye compound formed is' recovered by filtration. washed with water and dried. The dye compound obtained colors cellulose acetate silk a red shade.

Example 4 coupling reaction may be carried out as described in Example 3 The dye compound obtained colors cellulose acetate silk a red shade.

Example 5 21.9 grams of 1-amino-2-methyl-4-butylphenyl diketone are diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 13.5 grams of monoethyl-m-toluidine. The coupling reaction may be carried out as described in Example 3. The dye, compound obtained colors cellulose acetatesilk a rubine shade.

Example 6 23.3 grams of 1-amino-2-pentyl-4-methylphenyl diketone are diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 16.7 grams of ,8-hydroxyethyl-m-toluidine. Coupling may be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk a rubine shade.

Example 7 20.7 grams of,

CHI'

=0 CHS-E-QNHQ T OCH:

are diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 14.4 grams of 5,5-dimethyl-1,3-cyclohexadione. The coupling reaction may also be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk a greenish-yellow shade.

Example 8 1 20.5 grams of,

are diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 14.2 grams of l-methyl barbituric acid. The coupling reaction may be carried out as described in Example 2. The dye compound obtained colors cellulose acetate silk a greenish-yellow shade.

Example 9 28 grams of 1-amino-2-methyl-4-cyclohexylfi-carboxamidephenyl diketone are diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 16.7 grams of fl-hydroxyethyl-mtoluidine. The coupling reaction may be carried out as described in Example 3. The dye compound obtained colors oellulose acetate 2. red shade.

sodium chloride following which it may be re- Example 10 1 gram mole of 1-amino-2,4=-dimethyl-6-nitrophenyl diketone is diazotized and the diazonium compound obtained is coupled with 1 gram mole of 5-hydroxy dimethyl-m-naphthylamine.v The coupling reaction may be carried out in accordance with the method described in Example 3. The dye compound obtained colors cellulose acetate silk a blue shade.

Example 11 1 gram mole of I CaHn (cyclohexyl) is diazotized in accordance with the method described in Example 1 and the diazonium compound obtained is coupled with 1 gram mole of the sodium salt of sulfatoethylbutylaniline. The dye compound formed by the coupling reaction may be precipitated from solution by the addition of sodium chloride following which it may be recovered by filtration and then dried. The dye compound obtained colors cellulose acetate silk a rubine shade.

Example 12 1 gram mole of N02 OCHs C2115 is dissolved in a mixture of dioxane and pyridine and phenylphosphoryloxychloride (20% excess) is added dropwise with stirring at 10 C. Following this addition, the mixture is then slowly warmed to 60 C. over a period of four hours. Upon completion of the reaction, an aqueous solution of sodium carbonate is added until the mixture is just alkaline to litmus. Following the addition of the sodium carbonate, the dioxane and pyridine solvents are removedby distillation under reduced pressure and the residue remaining containing the desired dye compound is dissolved in hot water and filtered to remove impurities. The desired dye compound may be precipitated from the filtrate by the addition of covered by filtration and dried. The dye compound obtained is water-soluble and colors cellulose acetate silk a purple shade from an aqueous solution.

1 gram mole of 2,4-dimethylphenyl diketone azoethyl ,8 hydroxyethylaniline may be substituted for the dye compound of the above example to obtain a dye which hasthe formula:

M which colors cellulose acetate silk a red shade from its aqueous solution.

Example 13 are diazotized in accordance with the method described in Example 1 and thediazonium compound obtained is coupled with 22.4 grams of sodium-1-hydroxynaphthalene-5-sulfonate dissolved in a cold aqueous solution of sodium carbonate. Upon completion of the coupling reaction the mixture is made acid to Congo red paper and the dye compound formed, precipitated by the addition of sodium chloride, recovered by filtration, washed and dried. This dye compound has little or no affinity for organic derivatives of cellulose but colors wool and silk a red shade.

Color on cellulose Almne Coupling component acetate Silk CH3CHzCH2C NH: l-amino-2-methoxy-5-methylbenzene Wine.

(II) Di-fi-hydroxyethyl-aniline Rubine.

110013290 NH2 Difl-hydroxyethyl aniline ([5 Ethyl glyceryl-aniline Do.

' omoi-nomom SOaNHz 01134 NE? Mono ethyl-m-toluidine -Wine.

It will be understood that the dyes of Examples 1-12, inclusive, and of the tabulation color organic derivatives of cellulose, other than cellulose acetate silk, generally similar shades as indicated for cellulose acetate silk. Again, as previously indicated, these dyes color wool and silk generally similar shades as organic derivatives of cellulose.

The specific dye compounds shown or indicated herein are intended to be illustrative and not limitative of my invention. To illustrate, any of the diazo components disclosed herein may Amine Coupling component g gfi g N O 2 O H3 CHzCHOHCHaOH C H;C NH: N Violet.

ll O H C: C H:

Do Phenylmornhnl nn Rubine. Dn fi-hydroxy dimethyl-a-naphthylamim Blue.

5 5-dimethy1-1,g-cyclo-hnzadinnn Greenish-yellow. C Ha-C NH Batbiturle cid [I Ethyl-fl-hydl'ox'yethy'laniline Red. 0 Di-fl-hydroxyethylaniline Do.

I C Ha C H3(C H1) iii-(i NH: Monoglyceryl cresidinn Rubina.

no sin-( NH: DimethyI-a-naphthylamine Do.

1 :0 C H; /C:Hs

3-methy1-5 py1n7rflnnn Greenish-yellow. CHa-(J- NH: fi methylpyrnnnna D (H) Ethyl-m-tnlui rl i no Rubine.

0 H;(] NH; Mono-fl-hydroxyethylaniline Red.

g Methyl ethylaniline D0.

i= C 2H5 NHz- C-CH2CH=C H2 Monocyclohexylanilinn D [I Phenylmorpnnlenn Do. O O Ethyl glyceryl-Z,5-dimethoxyaniline Rubine. I 0 H3 0 .4? N11 Propyl glycery'lanilinn Red.

D0 Ethyl-glyceryl-m-chloroaniline D0. D0 Di fi-hydroxyethyl-a-naphthylamine Wine. Dn 3-hydroxy tetrahydroqninnlim Do, Do Tetra-hydro naphthoquinclinn Violet. Dn Sod um ethyl-fl-sulfatoethylaniline Red. Do Sodium butyl-fl-sulfoethyl nilin Do. D Phenyl morpholene. Do. Do 1-amino-2-methyl-5-methoxybenzene Do Do Ethyl-B-hydroxyethylanilinp Dn Di-fi-hydroxyethyl-m-hrnmnanilinn Do. D Dimethylaniline- Do.

be coupled with any of the coupling components shown herein to obtain dyes within the scope of my invention. Similarly, diazotized Lamina-2,4- dimethyl-G-sulfonic phenyl diketone, for example, can be coupled with the various coupling components disclosed herein to obtain dyes suited for the coloration of wool and silk.

In order that my invention may be fully understood, the preparation of a number of intermediate substances employed in the manufacture of the dye compounds of my invention is disclosed hereinafter.

Compounds having the. general formula:

i Ra wherein R3 has the meaning previously assigned to it may be prepared in accordance with .the general method described in J. prakt. chem. 2, vol. 130, at page 81(1.931). Compounds of the above general formula may be converted to aminoketones having the. general formula:v

by heating with an excess of ammonia water in an autoclave, with or without a catalyst such as finely divided nickel, at temperatures ranging between 150-300 C. These aminoketone's, which can be diazotized and employed in the production of the azo compounds of. my invention,can in turn be halogenated, nitrated or sulfonated, for example, in accordance with the methods described in J. Chem. Soc. 85, 340 (1904) ;.105, 125 (1914), p. 2403 (1931), J. Am. Chem. Soc. 50, 158 (1928), Ber. 65, 1334 (1932) and Org. Syn, Coll. Vol. 1, p. 78. i

The azo dye compounds of my invention-are, for the most part, relatively insoluble in water. Those compounds which are insoluble in water may be advantageously employed for the direct dyeing, of textile materials by grinding the dye to a fine powder, intimately mixing it with a suitable dispersing or-solubilizing agent, and adding the resulting mixture to water or av dilute solution of soap in water to form an aqueous dyebath. Following this known preparation of the dyebath, the textile materials to be dyed may be added to the dyebath and the dyeing operation conducted in known fashion. The dye compounds of my invention whichjare waterv soluble do notjof course, requirethe use of a dispersing or solubilizing agent but may be applied to silk, wool and (depending upon the nature and position of the water-solubilizing group) organic derivativesof cellulose textile materials from an aqueous, solution of .the dye which may contain salt. For amore complete description .as to how; the azo dye compounds of my invention may be employed in dyeing or coloring operations, reference may be had to McNally and Dickey U. S. Letters Patent No. 2,115,030, issued April 26, 1938. For a more detailed description as to how, the water soluble azo dyes of my invention may be employed for the coloration of textile materials made of or containing organic derivatives of cellulose, silk and wool or mixtures l of these, reference may be had to McNally and Dickey U. S. Letters Patent No. 2,107,898, issued February 8, 1938.

I claim:

1. The azo dye compounds having the general naphthalene, a hydroaromatic, and a: heterocyclic coupling component.

2. The azo dye compounds having the general formula:

R,-'-.N' ='NR1 wherein R represents the residue of an aryl nucleus; of the-benzeneseries containing two 2M4"); (-7 groups, wherein R'z-represents an alkyl group, an allyl group or a cycloalkylgroup, one in ortho and one in para position to the-azolbond and R1 represents the residue. of a hydroxyalkylamine of the benzene series. V

'3. The azo dye compounds having the general formula: v V n "N.=lNR1 wherein R representsthe residue of an a lyl nucleus of the benzene series containing two groups, wherein R2 representsan alkyl group, one.

in ortho and one in'para position to the azo bond and R1 represents the residue of a coupling component selected from the group consisting of a benzene, a naphthalena-a hydroaromatic,

and a heterocyclic coupling. component.

.4. They azo. dye compounds having the general formulaz I a v wherein Rrepresents'the residue of an 'aryl nugroupsgwherein R represents an'alkyl gr0ul ..one

, in ortho and one in para position to the azo bond and R1 represents the residue of a benzene coupling component. 5. The nuclear non-sulfonated azo dye compounds having the general formula:

wherein Rrepresents the residue of an aryl nucleus of the benzene-series containing. twoformula:

wherein R2 Ra each' represents a. member selected from the group consisting of an alkyl group, an allyl group and a cycloalkyl group and R1 represents the residue of a member selected from the group consisting of .a benzene nucleus,"

a naphthalene nucleus, a hydroaromatic nucleus and a heterocyclic nucleus.

wherein R2 and Rs each represents an alkyl group and R1 represents the residue of a hydroxyalkylamine of the benzene series.

9. The azo dye compounds having the general formula:

wherein R2 and R3 each represents a member selected from the group consisting of an alkyl group, an allyl group and a cycloalkyl group, R1 represents the residue of a coupling component selected from the group consisting of a benzene, a naphthalene, a hydroaromatic, and a heterocyclic coupling component and wherein X represents a member selected from the group consisting of a nitro group, a halogen atom, an alkoxy group, an alkyl group, an aryloxy group, a sulfonamide, a carboxamide, and an alkyl sulfone group.

10. The azo dye compounds having the general formula:

wherein R2 and R1 each represents an alkyl group, R1 represents the residue of a benzene coupling component and wherein X represents a member selected from the group consisting of a nitro group, a halogen atom, an alkoxy group, an alkyl group, an aryloxy group, a sulfonamide, a carboximide, and an alkyl sulfone group.

11. The nuclear non-sulfonated azo dye compounds having the general formula:

wherein R2 and R3 each represents an alkyl group, R1 represents the residue of a hydroxyalkylamine of the benzene series and wherein X represents a member selected from the group consisting of a nitro group, a halogen atom, an alkoxy group, an alkyl group, an aryloxy group, a sulfonamide, a carboxamide, and an alkyl sulfone group.

12. Material made of or containing an organic derivative of cellulose colored with a nuclear nonsulfonated azo dye compound having the general formula:

wherein R represents the residue of an aryl nucleus of the benzene series containing two groups, wherein R2 represents an alkyl group, one in ortho and one in para position to the azo bond and R1 represents the residue of a hydroxal kylamine of the benzene series.

14. A cellulose acetate colored with a nuclear non-sulfonated, azo dye compound having the general formula:

wherein R represents the residue of an aryl nucleus of the benzene series containing two R's-figroups, wherein R2 represents an alkyl group,

an allyl group or a cycloalkyl group, one in ortho and one in para position to the azo bond and R1 represents the residue of a coupling component selected from the group consisting of a benzene,

a naphthalene, a hydroaromatic, and a heterocyclic coupling component.

15. A cellulose acetate colored with a nuclear nonsulfonated azo dye compound having the general formula:

RN=NR1 wherein R represents the residue of an aryl nucleus of the benzene series containing two Ra -fl]- V o r I groups, wherein R2 represents an alkyl group, one in ortho and one in para position to the azo bond and R1 represents the residue of a hydroxyalkylamine of the benzene series.

JOSEPH B. DICKEY.

Patent No. 2,226,199.

CERTIFICATE OF CORRECTION.

. December 21L, 19LLO JOSEPH B. DICKEJY. v It is hereby certified that error appears in ,the printed specification of the above numbered patent requiring correction as follows; Page 1, second column, line 5, after "azo" insert dye-q line LL5, for "teterocy0li0" read --heterocyclic-'-; page 2, first column, line 17, for "O- 50 0." read --O- 5 C.; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th day of April, A. D. 1941.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

